Cyclopentenyl esters of 2-mercapto-2-thiono 1, 3, 2-dioxaphosphorinane and 1, 3, 2-dioxaphospholane acids



a number of O or 1.

UnitedtStates Patent CYCLQPENTENYL ESTERS 0F Z-MERfiAPTU-Z- THIQN'I) 1,3,2-DI)XAPHOPHQRWANE AND 1,3, Z-DIOXAIHUSPHGLANE ACIDS Jeffrey H. Bartlett, New Providence, N.J., assignor to R550 Research and Engineering Company, a corporation of Delaware No Drawing. Original application-Aug. 12, 1955, 8er. No. 528,112. Divided and this application Mar. 39, 1969, Ser. No. 18,474

2 tllaims. (tCl. 260-461) This invention relates to a new class of chemical compounds and more particularly. relates to cyclo-organo compounds of phosphorus and derivatives thereof. The invention also relates to methods of preparing such compounds and to the uses of such compounds, particularly as lubricant additives and as agricultural chemicals.

The new class of chemical compounds of this invention contains the following molecular structure:

where Y Y? and Y each represent a sulfur atom or an 7 oxygen atom and a is a number of value 001 1. The primary cyclo-organo compounds of phosphorus are pre-. pared by the reaction of dihydric organic compounds with phosphorus pentasulfide, phosphorus pentoxide,

phosphorus oxyhalide, phosphorus thiohalideor mixtures thereof. Derivatives of these primary cyclo-organo compounds of phosphorus, which are prepared by reacting the primary compound with olefinic compounds, h alogenated organic compounds, aldehydes, hydroxy organic compounds, epoxides, nitrogen bases, metal bases and the 7 V als asst Patented Dec. I 1964 "ice 2 V preparing the primary cyclo-organo phosphorus compounds of this invention are of two general types, namely:

Type I where the R radicals are selected from the group consisting of hydrogen atoms'and alkyl radicals having 1 to i Z-methyl-Z-nitro-1,3-propane diol.

like, are the preferred compounds of the present invention.

THE DIHYDRIC ORGANIC COMPOUNDS The dihydric organo compounds useful in preparing the primary cyclo-organo compounds of phosphorus contain the following molecular structure:

-d-Y n I [a].

where Y and each represent a sulfur atom or an oxygen atom, preferably an oxygen atom, and a represents In general it is preferred to use dihydric organic compounds having the following general 5 formula:

. organic radicals. These organic radicals'pr'eferably contain inthe ra'ngeof about 1 to 20 carbon atoirra r'nore preferably about 1 to 10 carbon atomsi It is particularly preferred-that the R radicals 'be'hydrog'en atoms or alkyl groups containing 1' to10, carbon atoms. The preferred dihydric organic compounds are those wherein the-R radicals are selected from the group consistingwof hydrogen atoms and methyl radicals. vIf desired, the R-radicals contain substituents such as halogen atoms, .jN O +CN,:

OR, COOH*and COOR groups. 7 '1 The preferred dihydric organiccompounds'i'useful THE PRIh/TARY CYCLO-ORGANO COMPOUNDS OF PHOSPHORUS The primary 'cyclo-organo phosphorus compounds which are prepared by the reaction of a dihydric organic compoundyas described above, or mixtures thereof, with phosphorus pentasulfide, phosphorus pentoxide, phosphorus oxyhalide, phosphorus thiohalide, or mixtures thereof contain the following molecular structure:

where A is either a halogen atom or a radical: of the formula I Y H V 1 and Y Y Y and Y are each a sulfur atom or an oxygen atom. The preferred primary cyclo-organo. phosphorus compounds have (the following general formula:

whe A 1 Y2 3 ya 2; 3 4 R5 s u p'. have the aforementioned definitions.

I These primary'cyclo-organo phosphorus. compounds may be preparedin accordance with the following 'chem- I ical equationsz- Y2 l l where X represents a halogen atom. It will be understood that mixtures of P 8 P POX and PSX (where X represents a halogen atom) in any combinations and proportions may be employed. The preferred halides are chlorides, the bromides being second choice. The primary cyclo-organo phosphorus compounds wherein A is a halogen atom may be hydrolyzed to replace the halogen atom with the radical OH.

The reaction between the dihydric organic compound and the inorganic phosphorus compound (i.e., P 5 P 0 POX or PSX is carried out using generally about 1 mole of the dihydric organic compound per mole of the phosphorus oxyhalide or phosphorus thiohalide, or using about 2 moles of the dihydric organic compound per mole of phosphorus pentasulfide or phosphorus pentoxide. The preferred inorganic phosphorus compound is phosphorus pentasulfide. These reactions may be carried out generally at temperatures in the range of about 30 C. to 150 C., preferably about 40 C. to 90 C. In general, the reaction will be complete after about 0.5 to 4 hours, usually after about 1 to 2 hours. This reaction may be carried out in the presence of an inert solvent such as benzene, toluene, tetralin, dioxane, naphtha, etc. It is desirable in carrying out the reaction to intimately mix the reactants. Upon completion of the reaction, it is preferred to filter the reaction product to remove any small amount of solid material present.

THE DERIVATIVES OF THE PRIMARY CYCLO- ORGANO PHOSPHORUS COMPOUNDS where Y Y, Y and'Y each represent a sulfur or oxygen atom. Preferably Y and Y represent oxygen atoms and Y and Y represent sulfur atoms. Z represents an organic or inorganic radical derived from an organic or inorganic compound, hereinafter described in greater detail, which is reacted with the primary cycloorgano phosphorus compound.

is a chloromethyl ether.

The preferred derivatives of this invention have the following general formula:

where the Rs, Ys, Z and a have their aforementioned definitions. Preferably Z is an organic radical containing about 1 to 24 carbon atoms, more preferably about 4 to 18 carbon atoms. The preferred compounds may be considered to be of two ditferent types, namely:

and Type II R t O s 4 R5- R P R o sz in V Preferably Z is an organic radical having 1 to 24 carbon atoms and selected from the group consisting of alkyl, aryl, aralkyl, alkoxy-alkyl, cyano-alkyl and alkylol radicals.

The following are specific classes of chemical compounds which may be reacted with the primary cycloorgano phosphorus compounds to produce useful derivatives thereof:

(1) Unsaturated Organic Compounds Included in this class of chemical compounds are olefinic and polyolefinic hydrocarbons. Substituted olefinic hydrocarbons such as those containing halogen atoms, nitro groups, primary, secondary and tertiary nitrogen atoms, alkoxy groups, ester groups, COOH groups, etc. may also be employed if desired. Specific examples of such unsaturated organic compounds include propylene, isobutylene, butadiene, isoprene, piperyline, styrene, chlorostyrene, nitrostyrene, vinyl ethyl ether, divinyl ether, vinyl acetate, vinyl caprate, vinyl oleate, isopropenyl acetate, acrylonitrile, methacrylonitrile, methyl methacrylate, methyl acrylate, maleic anhydride, maleic esters, maleamic acids, vinyl pyridine and vinyl ethylamine. Generally the derivatives are prepared by reacting about 1 mole of the unsaturated organic compound with about 1 mole of the primary cyclo-organo phosphorus compound, the reaction between the two compounds taking place between the radical A (where A is YH) of the primary cyclo-organo phosphorus compound and the double bond of the unsaturated organic compound. This reaction may be carried out at temperatures of about 0 to 200 C., preferably about 25 to C., and the reaction will be completed generally after about 0.5 to 10 hours, usually after about 1 to 2 hours. Solvents such as benzene, toluene and ether may be utilized in this reaction.

These olefin derivatives (which are esters) are particular1ypreferred compounds of the present invention. They have been found to be outstanding lubricating oil additives, being particularly effective as anti-oxidants and corrosion inhibitors.

(2) Halogenaterz' Saturated Organic Compounds A particularly useful type of compound of this class The chloromethyl ethers particularly preferred, which are prepared by reacting an general wherein R is an organic radical having about 1 to 24 carbon atoms, preferably an alkyl radical. Specific chloromethyl ethers which may be employed include methyl chloromethyl ether, ethyl chlorom'ethyl ether, isopropyl chloromethyl ether, butyl chloromethyl ether, n-amyl chloromethyl ether, isoarnyl chloromethyl ether, n-hexyl chloromethyl ether, isooctyl chloromethyl ether, isodecyl chloromethyl ether, tridecyl chloromethyl ether, isohexadecyl chloromethyl ether, octadecyl chloromethyl ether, bis chloromethyl ether of ethylene glycol. Still further, aryl compounds may also be used such as benzyl chloride, his chloromethyl benzene, bis chloromethyl toluene, etc. Other halogenated saturated organic compounds which may be employed include the following: methyl chloride, methyl bromide, methyl iodide, ethyl bromide, propyl bromide, butyl chloride, octyl bromide, isodecyl bromide, tridecyl bromide, bromoform and trimethylene bromide.

These halogenated saturated organic compounds may be reacted with the primary cyclo-organic phosphorus compounds wherein A is the radical -Y H. Preferably however, the primary cyclo-organic phosphorus compound is first converted to an ammonium salt or metal (e.g., sodium, potassium) salt which is then reacted with the halogenated compound in a double decomposition reaction. The double decomposition reaction is conveniently carried out at a temperature of about 25 to 200, preferably about 50 to 150 C. The reaction will be completed generally after about 2 to 20 hours,

usually about 3 to 8 hours. Generally about 1 mole of the halogenated saturated organic compound and 1 mole of the primary cyclo-organic phosphorus compound (or ammonium or metal salt thereof) will be employed.

(3) Aldehydes The aldehydes useful in preparing the phosphorus derivatives of this invention have the general formula /O R---()( Y H Where R is an organic radical containing about (R .150" C., preferably about 50 to 100 C. and the reaction will be completed generally after about 0.5 to 10 hours, usually after about 2 to 4 hours. Specific examples of aldehydes which may be employed include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, hexaldehyde, octaldehyde, chlorol and acrolein.

(4) Hydroxy Organic Compourtds The cyclo-organo compounds of phosphorus wherein A is a halogen atom may be reacted with hydroxy organic compounds, preferably monohydric organic compounds such as alcohols and phenols. Preferably these monohydric compounds are monohydroxy substituted hydrocarbons but, if desired, alcohols, phenols and the like containing nitro groups, nitroso groups, halogen atoms, nitrilo groups and the like may be employed. Thioalcohols and thiophenols may likewise be employed. Generally about 1 moleof the hydroxy organic compound will be reacted with about 1 mole of the cyclo-organo phosphorus compound. This reaction may be carried out at a temperature of about 25 to 200 C., preferably about 50 to 150 C., and will generally be complete after about 0.5 to 10 hours, usually after about 1 to 4 hours. Specific examples of hydroxy organic compounds which may be employed include methanol, ethanol, butanol,

' isooctanol, phenol, cresol, octyl phenol, nonyl phenol,

is then a hydrogen atom) to 20 carbon atoms, preferably about 0 (R is then'hydro'gen) to 10 carbon atoms. Preferably R is an allryl radical. About 1 mole of such aldehydes may be reacted with 1 mole of the cyclo-organo phosphorus compounds to produce a hydroxy derivative thereof having possibly the following formula:

These aldehydes are reacted with cyclo-organo compounds of phosphorus wherein A in the formula is a 1 radical of the formula Y H. This reaction may conveniently carried out at temperatures of about 0=;to

p-nitro phenol, o-m-nitro phenol, chlorophenol, diand tri-chlorophenol, 'pentachlorophenol, ethyl mercaptan, propyl mercaptan and mercaptobenzothiazole.

5 Epoxides Hydroxy esters of the cyclo-organo phosphorus compounds, may also be prepared by reacting the cycloorgano phosphorus compounds with epoxides employing generally a mole-for-mole ratio of the reactants. Alkylene oxides containing about 2 to 6, preferably about 2 to carbon atoms per molecule may be employed. Styrene oxide is also a very useful epoxide reactant. These epoxides may be reacted with cyclo-organo phosphorus compounds wherein A is a radical of the formula Y H. Specific examples of epoxides which may be employed include ethylene oxide, propylene oxide, butylene oxide, amylene oxide, styrene monoxide, butadiene monoxide and epoxides obtained from cyclohexane, butadiene polymers and copolymers, isoprene polymers, isobutyleneisoprene copolymers, oleic esters, terpenes, rubber latex.

Furthermore, pesticides, lube oil additives, etc., which possess an epoxide group may be improved by treatment with a cyclic d-ithiophosphoric acid, e.g., Dieldrin and Endrin treated with the dithiophosphoric acid from neopentyl glycol or ,8 butylene glycol. V

The reaction may be carried out at a temperature in the range of about 25 to 150, preferably about 50 to 100 C., and will be complete after about 0.5 to 4 hours, usually after about 1 to 2 hours. Preferably the reactants are intimately mixed during the reaction.

(6) Nitrogen Bases bases which may be employed include ammonia, methyl amine, dimethyl amine, trimethyl amine, ethylnamine,

diethyl amine, propyl amine, octyl amine, monoethanol amine, diethauol amine, triethanol amine, p-amino phenol,

6 p-phenylene diamine, diphenyl amine, pyridine, quinoline, guanidine.

The nitrogen bases may be reacted with cyclo-organo phosphorus compounds wherein A is a radical of the formula Y H or a halogen atom. The reaction between the phosphorus halide compounds of the present invention and nitrogen compounds possessing a hydrogen on the nitrogn atom may be carried out generally at a temperature of about 25 to 150 C., preferably about 50 to 125 C. and will be complete after about 1 to hours, usually after about 2 to 4 hours. The addition of ammonia or an amine to the dithiophosphoric acid will take place at room temperature.

(7) Metal Bases The cyclo-organo compounds of phosphorus may also be reacted with metal bases such as the oxides, hydroxides and carbonates. Preferred metal bases are those of the alkali metals, such as potassium and sodium, and alkaline earth metals such as calcium, barium and zinc. However, other metals such as aluminum, lead, iron, nickel, cadmium and the like may be employed.

Generally about b moles of the cyclo-organo phosphorus compounds will be reacted with 1 mole of the metal base, where b represents the valence of the metal. This reaction can be conveniently carried out at temperatures of about 50 to 200 (3., preferably about 60 to 125 C., and will be complete after about 1 to 12 hours, usually about 2 to 6 hours. The derivatives so produced which are metallo-organic compounds of phosphorus have the following general formula:

especially exemplified in the oxidation of the dithiophosphoric acid to its disulfide, e.g.

Such an oxidation may be effected by the use of air, H202, NaNO +H SO HNO3, C12, etc.

A trisulfide may be produced by reaction of the dithiophosphoric acid with SCl e.g.

In like manner a tetrasulfide may be produced by use of S 01 It may also be possible to reduce the amount of sulfur by formation of the monosulfide through treatment with NaCN,e.g.

The dithiophosphoric acid also readily reacts with carboxylic acid chlorides, sulfonyl chlorides, isocyanates, S001 SC CI POCI PO1 etc. to yield valuable products.

USES OF THE CYCLO-ORGANO PHOSPHORUS COMPOUNDS AND DERIVATIVES THEREOF The present class of compounds, asd particularly the derivatives of the primary cyclo-organo phosphorus compounds, are useful as lubricant additives, particularly as oxidation-corrosion inhibitor additives for lubricating oil compositions. Generally the lubricating oil compositions of the present invention will comprise a major proportion of a lubricating oil and a minor corrosion inhibiting amount of the novel compounds of this invention, preferably the derivatives of the primary cyclo-organo phosphorus compounds. Generally about 0.01 to 10%, and preferably about 0.1 to 3% by weight, based on the total composition, of the present compounds will be employed in the lubricants.

The lubricating oil base stocks used in the compositions of this invention may be straight mineral lubricating oils or distillates derived from parafiinic, naphthenic, asphaltic or mixed base crudes, or if desired, various blended oils may be employed as well as residuals, particularly those from which asphaltic constituents have been carefully removed. The oils may be refined by conventional methods using acid, alkali and/or clay on other agents such as aluminum chloride, or they may be extracted oils produced for example by solvent extraction with solvents of the type of phenol, sulfur dioxide, furfural, dichloroethyl ether, nitrobenzene, crotonaldehyde, etc. Hydrogenated oils or White oils may be employed as well as synthetic oils prepared, for example, by the polymerization of olefins or by the reaction of oxides of carbon with hydrogen or by the hydrogenation of coal or its products. In certain instances cracking coal tar fractions and coal tar or shale oil distillates may also be used. Also for special applications variou organic esters or animal, vegetable or fish oils or their hydrogenated, polymerized or voltolized products may be employed, either alone or in admixture with mineral oils.

Synthetic lubricating oils having a viscosity of at least 30 SSU at F. may also be used, such as esters of monobasic acids (e.g. ester of C Oxo alcohol with C Oxo acid, esten of C OX0 alcohol with octanoic acid, etc.), esters of dibasic acids (e.g. di-Z-ethyl hexyl sebacate, di-nonyl adipate, etc.), esters of glycols (e.g. C 0x0 acid diester of tetraethylenc glycol, etc.), complex esters (e.g. the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethyl-hexanoic acid, complex ester formed by reacting one mole of te-traethylene glycol with two moles of sebacic acid and two moles of 2-ethyl hexanol, complex ester formed by reacting together one mole of azelaic acid, one mole of tetraethylene glycol, one mole of C Oxo alcohol, and one mole of C Oxo acid), esters of phosphoric acid (e.g. the ester formed by contacting three moles of the mono'methyl ether of ethylene glycol with one mole of phosphorus oxychloride, etc.), halocarbon oils (e.g. the polymer of chlorotrifluoroethylene containing twelve recurring units of chlorotrifluoroethylene), alkyl silicates (e.g. methyl polysiloxanes, ethyl polysiloxanes, methyl-phenyl polysiloxanes, ethylphenyl polysiloxanes, etc.), sulfite esters (e.g. ester in the form of sprays, such as in aqueous dispersions of dust compositions of the active ingredient with a powdered clay.

Since the compounds of this invention are insoluble in water, it is preferable to use them admixed with wetting or emulsifying agents so as to be able to secure aqueous any of the above in any proportions. Mixtures of these synthetic oils and mineral oils may likewise be used.

For the best results the base stock chosen should normally be that oil which without the new addition agents v present gives highly satisfactory performance in the service contemplated. However, since one advantage of the agents is that their use also makes feasible the, employment of less satisfactory mineral oils or other oils, no strict rule can be laid down for the choice of the base stock. Certain essentials must of course be observed.

The oil must possess the viscosity and volatilitycharacteristics known to be required for the service contemplated. The oil must be a satisfactory solvent for the addition agent, although in some cases auxiliary solvent agents may be used. The lubricating oils, however they may have been produced, may vary considerably in viscosity and other properties depending upon the particular use for which they'iare desired, but they usually range from about 40 to 150 seconds Saybolt viscosity at 210 F. For the lubrication of certain low and medium speed diesel engines the general practice has often been to use a lubricating oil base stock prepared from naphthenic or aromatic erudes and having a Saybolt viscosity at 210 F. of 45 to 90 seconds and a viscosity index of to 50. However, in certain types of diesel service, particularly with high speed diesel engines, and in aviation engine and other gasoline engine service, oils of higher viscosity index are often preferred, for example, up to 75 to 100, or even higher viscosity index.

In addition to the/materials to be added according to the present invention, other agents may also be used such as dyes, pour depressors, heat thickened fatty oils, sulfurized fatty oils, organo metallic compounds, metallic or other soaps, sludge dispersers, foam suppressing agents, anti-oxidants, thickeners, viscosity index improvers, oiliness agents, resins, rubber, olefin polymers, voltolized fats, voltolized mineral oils, and/or voltolized waxes and colloidal solids such as graphite or zinc oxide, etc. Specific examples of such other compounds include dibenzyl disulfide, sulfurized sperm oil, voltolized sperm oil, phenyl alpha naphthylamine, polyisobutylene, polymerized lauryl methacrylate, diamyl trisulfide, sulfurized wax olefins, tricresyl phosphate, 2, 6-di-tert. butyl-4-methyl phenol, and the reaction product of phenol with sulfur chloride treated diisobutylene. Solvents and assisting agents, such as esters, ketones, alcohols, thioalcohols, amines, aldehydes, halogenated or nitrated compounds, and the like, may also be employed.

The present compounds are also useful additives (especially as anti-oxidants and corrosion inhibitors) in other mineral and synthetic products such as, for example, petroleum oil distillate products, e.g., gasoline, heating oil, diesel oils; greases, Waxes, asphalts, flushing oils, cutting oils, solvent oils, transformer oils and the like.

Generally useful concentrations of the present compounds in these products are in the range of about 0.01 to 5.0% by weight based on the total composition.

The present compounds are also useful as parasiticidal agents, that is, generally as agricultural chemicals. They are particularly effective as insecticides, fungicides, herbicides, plant defoliants and the like. Preferably the com- 7 pounds of this invention which are employed for these applications are the derivatives, particularly the olefin derivatives (esters), of the'primary cyclo-organo phosphorus compounds.

' The'compounds of this invention which in most cases are viscous liquids (generally), are best distributed tration of active ingredient in the aqueous emulsions varies with the insect pests to be treated. In general, the

aqueous emulsion contains about 0.0000lto 10% active ingredient, and about 0.1 to 5% wetting agent by weight.

The active compounds of this invention may also desirably be made up in solid compositions. A dust composition containing about 1 to 10 weight percent active ingredient is made up by admixing the active compounds with clays such as fullers earth, china clay, kaolin, or bentonite. .Solid wettable powders for aqueous dispersion contain about 60 to active ingredient, 20 to 40% clay, and about 0.1 to 5% wetting agent. Clay itself also acts as a spreading agent.

Among the water soluble wetting agents that can be used are the sulfates of long chain alcohols such as dodecanol up to octadecanol, sulfonated amide and ester derivatives, sulfonated aromatics, and mixed alkyl-aryl sulfonatederivatives, esters of fatty acids such as the ricinoleic acid ester of sorbitol, and petroleum sulfonates of C to C length. The non-ionic emulsifying agents such as the ethylene oxide condensation products of alkylated phenols may also be used. Y

Solvents for the compounds of this invention may be utilized as auxiliary agents if desired. Among the solvents for the compounds of this invention are: naphtha,

and the various fish poisons, also organic insecticides, such as di(p-)chlorophenyl-trichloroethane, benzene-hexachloride, and similar products may also be advantageously added.

The invention will be more fully understood by reference to the following examples. It is pointed out, however, that the examples are given for the purpose of illustration only and are not to be construed as limiting the scope of the present invention in any way.

EXAMPLE I.--PREPARATION OF DI'IHIOPHOSPHORIC ACID OF BETA BUTYLENE GLYCOL A dithiophosphorio acid having the following structural formula g. of the .crude-dithiophosphoric acid having an Acid EXAMPLE II.PREPARATION OF DITHIOPHOSPHORIC ACID OF NEOPENTYL GLYCOL A dithiophosphoric acid having the following structural formula was prepared as follows: A liter i -necked flask equipped with a stirrer, condenser and thermometer was charged with 936 g. (9 In.) neopentyl glycol and 1500 cc. benzol. This mixture was heated to 45 C. when 999 g. (4.5 m.) P 5 was added gradually during 20 minutes. Suflicient heat was applied to raise the temperature to 65 C. where it was held for minutes. Then the mixture was gradually heated to 85 C. during the next 45 minutes making a total reaction time of 1 hour and minutes. This was filtered hot through Hyflo leaving about 75 g. of unreacted P 8 The benzol was removed from the reaction product under reduced pressure with a final pot temperature of 145 C. at 4.0 mm. leaving a yield of 1782 g. of crude dithiophosphoric acid having an Acid No. of 0.442 ceq./ g. (87.5% pure).

- A 500 g. sample of the above crude product was distilled in a short path still as follows:

1 Essentially the dithiophosphoric acid shown above.

EXAMPLE III.PIEPARATION OF DITHIOPHOS- PHORIC ACID OF P INACOL A dithiophosphoric acid having the following structural formula was prepared as follows: A 5 liter 4-necked flask equipped with a stirrer, condenser and thermometer was charged with 1064 g. (9 m.) pinacol and 1500 cc. benzol. After heating to 40 C. there was added 999 g. P 8 during 5 minutes. Then the mixture was heated to 75 C. during the next 15 minutes. It was maintained at 75 to 90 C. for the next hour making a total reaction time of 1 hour and 20 minutes. After cooling to 70 C., the mixture was filtered through Hyflo leaving approximately g. of unreacted P 5 The benzol was then removed under reduced pressure in a short path still with a final pot temperature of 100 C. at 3.5 mm., leaving a yield of 1814 g. of crude dithiophosphoric acid. Acid No.=0.452 ceq./gm.

EXAMPLE IV.PREPARATION OF DERIVATIVE A An isobutylene ester of the dithiophosphoric acid of beta butylene glycol and having the following structural formula was prepared as follows: A 1" x 12" test tube was charged with 100 g. of the dithiophosphoric acid of beta butylene glycol. Isobutylene was injected through a porous tube for 1 /2 hours beginning at 25 C. and gradually raising the temperature to C. There was an increase in weight of 25 g. or a yield of 125 g. of the isobutylene ester.

EXAMPLE V.PREPARATION OF DERIVATIVE B A styrene ester of the dithiophosphoric acid of beta butylene glycol having the following structural formula was prepared as follows: A 500 cc. Erlenmeyer flask was charged with g. of the dithiophosphoric acid of beta butylene glycol and 70 g. styrene. There was a heat of reaction which caused the temperature to rise from an initial of 25 C. to 45 C. Within 10 minutes. The reaction was completed by heating on the steam bath for 1 hour and then allowing to stand overnight at room temperature. The unreacted styrene was removed by stripping in a short path still to a pot temperature of 100 C. at 2.0 mm. Yield of styrene ester=142 g.

EXAMPLE VI.PREPARATION OF DERIVATIVE C A chloromethyl ether (of C Oxo alcohol) derivative of the dithiophosphoric acid of neopentyl glycol having the following structural formula C. pot temperature at 1 mm. mercury pressure. Yield: 126 g.

Analysis:

Element- Percent H 9.33 C 54.47 S 15.17 P 7.17

The tridecyl chloromethyl ether used in this example was prepared as follows:

A S-Iiter, 4-neclzed flask equipped with a stirrer, condenser, thermometer and a porous glass gas inlet tube was charged with 2600 g. (13 moles) C Oxo alcohol and 420 g. paraformaldehyde. After cooling to 5 C. HCI gas was injected into the mixture for 4 hours with the EXAMPLE VII.PREPARA=TION OF DERIVATIVE D A methacrylonitrile ester of the dithiophosphoric acid of pinacol having the following structural formula CH3. CH3'(BO was prepared as follows: Pinacol dithio'phosphoric acid (106 g, 0.5 mole) was melted, then'allowed to cool to 50 C. at which temperature it started to crystallize. Freshly distilled methacrylonitrile (43 g., 0.64 mole) was added with stirring. Thetemperature rose spontaneously to 80 C. and was maintained at 70-80 1C., first =by coo of the pziraformalde ing, then by heating, for twenty minutes. The product was vacuum stripped to 85 C. at 1 mm. mercury pressure. The resulting residue (133 g.) was a light yellow oil having essentially the formula shown above.

0 EXAMPLE VIII.PREPARATION OF DERIVATIVE n A cyclopentenyl ester of the dithiophosphoric acid of neopentyl glycol having the following structural formula Coach? g l nl 0 s was preparedas follows: A 1-1iter round bottom flask termined by interpolation of the data obtained in the various periods.

Oil or oil blend: Bearing corrosion life (hrs) Base Stock Y 13 Base Stock+0.5 wt. percent of Derivative A 33 Base Stock+0.5 wt. percent of Derivative B 35 Base Stock+0.5 wt. percent of Derivative C 34 Base Stock+0.5 wt. percent of Derivative D 39 Base Stock+0.5 wt. percent of Derivative E 36 Base Stock+0.5 wt. percent of Derivative F 35 was charged with 96 g. of crude dithiophosphoric acid of neopentyl glycol, 100 g. benzol and 40 g. cyclopentadiene at 25 C. Within 10 minutes the heat of reaction had raised the temperature to 60 C. It .wasthen placed on the steam bath for an hour, after which it wasallowed to stand at room temperature overnight. The product was then stripped to a pot temperature of ll0 C 'at' 3.0 mm.

Yield= 125 g. 1

, EXAMPLE lX.-PREPARATION 0F. DERIVATIVE. F

A styrene ester of the dithiophosphoric acid of neopen tyl glycol having the following structural formula a 1 'H '0 v s CH3JZ +CH3 ple during. the test.

l4 EXAMPLE X t The derivatives prepared in Examples 1V to IX (Derivatives A, B, C, D, E-and F) were then evaluatedas oxidation-corrosion inhibitors in a standard bearing corrosion test, the derivatives being each evaluated at a concentration of 0.5% by weight in a-rnineral lubricating oil base stock (hereinafter referred to as Base Stock). The Base Stock was a phenol extracted-an solvent dewaxed mineral lubricating oil having a viscosity of about 66.0 SUS at 210 C. and a viscosity index of about 103, and was derived from Mid-Continent crude oil.

The vcorrosion test which was employed to evaluate Derivatives A to F, as Well as the Base Stock alone, was carried out as follower 500 cc. of the oil was placed in a glass oxidation tube (13 inches long and 2% inches in diameter) fitted at the bottom witha inch air inlet tube perforated to facilitate air distribution. The oxidation tube was then immersed in a heating bath so that the oil temperature was maintained at 325 vF. during the test. Two quarter sections of-automotive bearings of copperlead alloy of known weight having a total area of 25 sq. cm. Were attached to opposite sides of a stainless steel rod which was then immersed in the test oil and rotated at V .600 r. .p.m., thus providing sufficient agitation of the sam- Air was then blown through the oil at the rate of '2 cu. ft. per hour. At the end of each 4- hour period the hearings were removed, washed with naphtha and weighed todetermine the amount of loss by corrosion. The bearings were then repolished (to increase the severity of the test), rewei-ghed, and then subjected to the test for additional 4-hour periods in like manner. Theresults are given in the. following table as corrosion life, which indicates the number of hours required for the hearings to lose 100 mg. in Weight, de-

It will be noted that addition of Derivatives A to F of the present invention substantially increased the bearing life. More specifically, the bearing life was increased to about threefold the original value by the addition of only 0.5 weight percent of each of the Derivatives A to F.

EXAMPLE XI.PREPARATION OF DITHIOPHOSPHORIC ACID OE 2-ETHYL-2-BUTYL PROPANE DIOL-1,3

The dithiophosphoric acid of 2-ethyl-2-butyl propane diol-l,3-having the following structural formula with 1280 g. '(8 in.) Z-ethyl, 2-bi1tylpropane diol-l,3 and i pentyl glycol and g. styrene. WithinllO minutes the temperature rose from an initial of 25 C. to 77 C. The

temperature of -95 C. at l.0 mm. Yield of .styrene flaslewasrthen placed/ the steam bath for 2 1 after'which the reaction productwas strippedgto a pot with a stirrer, condenser and thermometer was charged 1000 cc. benzoly, This was heated to 55 C. and then 888 g. (4 rh.) IP S was added during 5 minutes. The

temperature was then. raised to C. andheld at 70 C.

to C. for 1 hour, after which the product was filtered through Hyfio. There .was-a residue-oi about. 50g. of. unreacted P 3 The benzol was removed under reduced pressure finally hcatin'g {to [a pot temperature v.of C.

1 at 401A yield of 1906 g. ofcrude dithio'phosphoric 'acid was obtained having an Acid No. of 0. 338 ceq/gm.

EXAMPLE XIL-PREPARATION OF DERIVATIVE G The isobutyl ester of the dithiophosphoric acid of 2- ethyl-2-butyl propane diol-l,3 having the structural formula Was prepared as follows: A 1" x 12" test tube was charged with 100 g. of the dithiophosphoric acid of 2-ethyl-2- butyl propane diol-1,3 and then isobutylene was injected into it thorugh a porous tube at 60 to 80 C. for 2 hours. Yield of isobutyl ester: 1 19.5 g.

The following additional derivatives were also prepared: (1) the acrylonitrile, methacrylonitrile, isobutylene, methyl methacrylate, ethylene oxide, propylene oxide, butadiene and epichlorhydrin derivatives of the dithiophosphoric acid of neopentyl glycol; (2) the styrene, isobutylene and cyclopentadiene derivatives of the dithiophosphoric acid of 2-ethyl2-butyl propane diol-1,3; (3) the acrylonitrile, methacrylonitrile, cyclopentadiene, and epichlorhydrin derivatives of the dithiophosphoric acid of 2,3 butane diol; (4) the styrene, acrylonitrile, isobutylene, cyclopentadiene, vinyl acetate, methyl methacrylate, butadiene monoxide and epichlorhydrin derivatives of the dithiophosphoric acid of pinacol.

This is a division of US. application Serial No. 528,- 112, entitled Cyclo-Organo Compounds of Phosphorus, filed August 12, 1955.

What is claimed is:

1. A compound of the formula 1 6 where R R R R R and R are each mmebers selected from the group consisting of hydrogen atoms and alkyl radicals containing 1 to 10 carbon atoms, and a is a whole number of value 0 to 1.

2. -A compound of the formula References Cited in the file of this patent UNITED STATES PATENTS 2,596,076 Hook et a1 May 6, 1952 2,611,728 Bartlett et a1. Sept. 23, 1952 2,661,365 Gamrath et a1 Dec. 1, 1953 2,661,366 Gamrath et al Dec. 1, 1953 2,744,128 Morris et a1. May 1, 1956 2,841,605 Lanham July 1, 1958 2,842,527 Melamed July 8, 1958 2,843,586 Melamed July 15, 1958 2,859,086 Feild et al Nov. 4, 1958 2,876,244 Lanham Mar. 3, 1959 2,876,245 Lanham Mar. 3, 1959 2,892,862 Lanham June 30, 1959 2,900,407 Lanham Aug. 18, 1959 2,903,474 Lanham Sept. 8, 1959 3,006,946 Lanham Oct. 31, 1961 3,020,305 Chupp Feb. 6, 1962 3,021,354 Lanharn Feb. 13, 1962 3,028,302 Chupp Apr. 3, 1962 OTHER REFERENCES Arbuzov et al.: Chem. Abst., vol. 42, C01. 4932-4934 (1948).

Arbuzov et al.: Chem. Abst., vol. 45, col. 1512-1513 

1. A COMPOUND OF THE FORMULA 